In situ ultrasonic measurements: a powerful tool to control the synthesis of zeolites from coal fly ash

An in situ ultrasonic diagnostic technique was applied to monitoring the hydrothermal synthesis of zeolite A and X of clear solution extracted from alkaline fused class F coal fly ash. In this context, kinetic evaluations based on in situ ultrasonic diagnostic data displayed an important approach to study the synthesis process. The impact on nucleation and crystal growth was demonstrated by variation of a few relevant parameters such as reaction temperature, amount of water, Na₂O and ageing time, including templated colloidal synthesis mixtures as model solution. To complement the kinetic analysis, ex situ techniques such as ICP, X-ray diffraction, scanning electron microscopy and dynamic light scattering were used to investigate liquid phase and reaction products extracted from the reaction mixture during the synthesis.     

Intrinsic Kinetics of Dimethyl Ether Synthesis from Syngas

The intrinsic kinetics of dimethyl ether (DME) synthesis from syngas over a methanol synthesis catalyst mixed with methanol dehydration catalyst has been investigated in a tubular integral reactor at 3-7MPa and 220-260℃. The three reactions including methanol synthesis from CO and H2, CO2 and H2, and methanol dehydration were chosen as the independent reactions. The L-H kinetic model was presented for dimethyl ether synthesis and the parameters of the model were obtained by using simplex method combined with genetic algorithm. The model is reliable according to statistical analysis and residual error analysis. The synergy effect of the reactions over the bifunctional catalyst was compared with the effect for methanol synthesis catalyst under the same conditions based on the model. The effects of syngas containing N2 on the reactions were also simulated.     

Kinetics modeling for the mixed reforming of methane over Ni-CeO2/MgAl2O4 catalyst

Kinetics model was developed for the mixed (steam and dry) reforming of methane, which is useful for the control of H2/CO ratio. The equilibrium constants of reaction rate were determined using the experimental equilibrium data at different reaction temperatures, while the forward reaction rate constants were estimated using the experimental data under non-equilibrium (high inert fraction and high space velocity) conditions. The comparison between calculated and experimental data clearly showed that the developed model described satisfactorily, and further analysis using the parametric sensitivity determined the wall temperature and CO2 fraction in the feed gas as effective parameters for the manipulation of CH4 conversion and H2/CO ratio of synthesis gas under the equilibrium condition. Meanwhile, the inert fraction, rather than the residence time, was selected as additional parameter under non-equilibrium condition.     

Synthesis monitoring of SBA-15 nanostructured materials

The SBA-15 materials were synthesized by the hydrothermal method using tetraethyl orthosilicate as silica source and P123 as template agent. The synthesis process was accomplished varying the time during the hydrothermal processing. For the synthesis monitoring, a small amount of sample was removed at different times, and analyzed by thermal analysis in order to determine the temperature ranges related to water desorption, template decomposition and silanol condensation for the SBA-15 nanostructured materials, as well as to estimate their quality. The samples were characterized by X-ray diffraction, infrared absorption spectroscopy, scanning electron microscopy, BET surface area and pore size distribution. The activation energy relative to decomposition of P123 template was determined from TG curves, using multiple heating rates and applying the model free kinetics. From the obtained data, it is possible to monitor the hydrothermal synthesis of SBA-15 in order to control the properties and conditions to prepare ordered materials.     

Hollow silica spheres with an ordered pore structure and their application in controlled release studies

Herein we report the synthesis and characterization of hollow silica spheres with a narrow size distribution, uniform wall thickness, and a worm-like pore structure. The formation of these spheres was monitored by confocal laser scanning microscopy and dynamic light scattering. A model for the molecular build-up of these silica hollow spheres is derived from these data in combination with studies of the as-made particles by transmission electron microscopy, scanning electron microscopy, pore size analysis, thermogravimetric analysis, and solid-state nuclear magnetic resonance. We further demonstrate that these spheres can be used for the encapsulation and subsequent release of different dye molecules.     

Size-controlled synthesis and characterization of thiol-stabilized gold nanoparticles

Size-controlled synthesis of nanoparticles of less than a few nanometers in size is a challenge due to the spatial resolution limit of most scattering and imaging techniques used for their structural characterization. We present the self-consistent analysis of the extended x-ray absorption fine-structure (EXAFS) spectroscopy data of ligand-stabilized metal nanoclusters. Our method employs the coordination number truncation and the surface-tension models in order to measure the average diameter and analyze the structure of the nanoparticles. EXAFS analysis was performed on the two series of dodecanethiol-stabilized gold nanoparticles prepared by one-phase and two-phase syntheses where the only control parameter was the gold/thiol ratio xi, varied between 6:1 and 1:6. The two-phase synthesis resulted in the smaller particles whose size decreased monotonically and stabilized at 16 A when xi was lowered below 1:1. This behavior is consistent with the theoretically predicted thermodynamic limit obtained previously in the framework of the spherical drop model of Au nanoparticles.     

Total Synthesis,Stereochemical Revision,and Biological Assessment of Iriomoteolide-2a

Iriomoteolide-2a is a marine macrolide metabolite isolated from a cultured broth of the benthic dinoflagellate Amphidinium sp. HYA024 strain. This naturally occurring substance was reported to show remarkable cytotoxic activity against human cancer cell lines HeLa and DG-75 and in vivo antitumor activity against murine leukemia P388 cell line. Herein, the total synthesis, stereochemical revision, and biological assessment of iriomoteolide-2a are reported in detail. Total synthesis of the proposed structure 1 of iriomoteolide-2a featured a late-stage convergent assembly of three components by a Suzuki–Miyaura coupling, an esterification, and a ring-closing metathesis. However, the NMR data of synthetic 1 were not identical to those of the natural product. Careful analysis of the NMR data of the authentic material and synthesis/NMR analysis of appropriately designed model compounds led to consideration of four possible stereoisomers 2 – 5 as candidates for the correct structure. Accordingly, total syntheses of 2 – 5 were achieved by taking advantage of the convergent strategy, and comparison of the NMR spectra of synthetic 2 – 5 with those of the natural product led to the conclusion that 5 shows the correct relative configuration of iriomoteolide-2a. The absolute configuration of this natural product was finally established through chiral HPLC analysis of synthetic 5 /ent- 5 with the authentic sample. The antiproliferative activity of the synthetic compounds was assessed against HeLa and A549 cells to show that, in contrast to expectation, synthetic 5 and ent- 5 were only marginally active in these cell lines. This work clearly underscores the vital role of total synthesis in the establishment of the structure and biological activity of natural products.     

化学反应处理的计算模型

介绍了一种将同类反应上升为合成反应知识和在计算机上实现反合成分析的方法,反合成分析是合成设计中最关键的一步,在本工作中采用了基于谋略键寻找的合成设计方法。它有逻辑宜于在计算机上实现的优点。为了实现这个方法,我们首次提出了一种能中肯地描述合成反应的计算模型—反应知识的分类模型。这一模型由三条规则定义：规则A-反应类型;规则B-发生反应的外部条件;规则C-不适宜采用这个反应的情况;这种计算模型能够将海量反应数据中最重要最基本的信息提炼出来,转换成计算机能处理的知识。它也包含有反应适用范围的信息,从而提高了析分过程的外推能力。     

Prediction of the antimicrobial activity of quaternary ammonium salts against Staphylococcus aureus using artificial neural networks

The study of the quantitative structure–activity relationship (QSAR) on antibacterial activity in a series of new imidazole derivatives against Staphylococcus aureus was conducted using artificial neural networks (ANNs). Antibacterial activity against S. aureus was associated with a number of physicochemical and structural parameters of the examined imidazole derivatives. The designed regression and classification models were useful in determining the antibacterial properties of quaternary ammonium salts against S. aureus. The developed models of artificial neural networks were characterized by high predictability (93.57% accuracy of classification, regression model: training data R = 0.92, test data R = 0.92, validation data R = 0.91). ANNs are considered to be a useful tool in supporting the design of synthesis and further biological experiments in the logical search for new antimicrobial substances. Data analysis using ANNs enables the optimization and reduction of labor costs by narrowing the compound synthesis to achieve the desired properties.     

Pd-Cu/La0.5Pb0.5MnO3催化合成碳酸二苯酯的宏观动力学研究

随着聚碳酸酯在机械制造、电子、军事、安全及光纤通讯业等领域的广泛应用,其生产所需原料碳酸二苯酯(Diphenyl carbonate简称DPC)的合成越来越被世人所关注.……     

Synthesis and adsorption on gold surfaces of a functionalized thiol: elaboration and test of a new nitroaromatic gas sensor

A new type of sensor was built by synthesizing a long-chain thiol functionalized with an aromatic head group and grafting it onto a gold surface. The synthesis route is here described, together with the IR, MS, and RMN analysis of the new product. Adsorption of the latter onto gold was assessed by a combination of RAIRS and XPS data. Those reveal that a monolayer of thiol is adsorbed and oriented with the benzene groups toward the external part of the layer. Detection tests were performed in various atmospheres by QCM. The response shows good sensitivity to 2,4-dinitrotrifluoromethoxybenzene as a model of nitroaromatic compound.     

A kinetic study of synthesis of amoxicillin using penicillin G acylase immobilized on agarose

We presenta kinetic model for the synthesis of amoxicillin from p-hydroxyphenylglycine methyl ester and 6-aminopenicillanic acid, catalyzed by penicillin G acylase immobilized on agarose, at 25°C. Michaelis-Menten kinetic parameters (with and without inhibition) were obtained from initial velocity data (pH 7.5 and 6.5). Amoxicillin synthesis reactions were used to validate the kinetic model after checking mass transport effects. A reasonable representation of this system was achieved under some operational conditions, but the model failed under others. Nevertheless, it will be useful whenever a simplified model is required, e.g., in model-based control algorithms for the enzymatic reactor.     

Use of Raman spectroscopy as an in situ tool to obtain kinetic data for organic transformations

Raman spectroscopy has been used as an in situ tool to obtain kinetic data for an organic transformation. The model reaction studied was the synthesis of 3-acetylcoumarin from the condensation between salicylaldehyde and ethyl acetoacetate with piperidine as a catalyst. The study shows that precise kinetic data can be obtained quickly and reproducibly, allowing for the facile determination of both overall reaction order and reaction order with respect to each component of the reaction. Additionally, Arrhenius parameters such as activation energy for a reaction can be readily obtained. In conjunction with computational modeling, this data-rich analysis technique also allows for in-depth probing of mechanistic aspects of reactions. Microwave heating proves to be an ideal tool for aiding in kinetic studies. It offers reproducible noncontact heating as well as precise temperature monitoring and data recording.     

Predicting neopentane isosteric enthalpy of adsorption at zero coverage in MCM-41

The isosteric enthalpy of adsorption for neopentane at relative pressures down to 3 × 10(-8) in MCM-41 was predicted for the temperature range from -15 to 0 °C. At such low pressures and temperatures, experimental measurements become problematic for this system. We used an atomistic model for MCM-41 obtained by means of a kinetic Monte Carlo method mimicking the synthesis of the material. The model was parametrized to represent experimental nitrogen adsorption isotherms at 77 K using grand canonical Monte Carlo simulations. The simulated isosteric enthalpy of adsorption shows very good agreement with available experimental data, demonstrating that GCMC simulations can predict heats of adsorption for conditions that are challenging for experimental measurements. Additional insights into the adsorption mechanisms, derived from energetic analysis at the molecular level, are also presented.     

Cornforth–Evans Transition States in Stereocontrolled Allylborations of Epoxy Aldehydes

Allylboration reactions rank among the most reliable tools in organic synthesis. Herein, we report a general synthesis of trifunctionalized allylboronates and systematic investigations of their stereocontrolled transformations with substituted aldehyde substrates, in order to efficiently access diverse, highly substituted target substrates. A peculiar transition in stereocontrol was observed from the polar Felkin–Anh (PFA) to the Cornforth–Evans (CE) model for alkoxy- and epoxy-substituted aldehydes. CE-type transition states were uniformly identified as minima in advanced, DFT-based computational studies of allylboration reactions of epoxy aldehydes, conforming well to the experimental data, and highlighting the underestimated relevance of this model. Furthermore, a mechanism-based rationale for the substitution pattern of the epoxide was delineated that ensures high levels of stereocontrol and renders α,β-epoxy aldehydes generally applicable substrates for target synthesis.     

Synthesis and characterization of silicate polymers

In this work an inorganic polymer is developed based on Elkem microsilica and potassium hydroxide. Using experimental data and the partial charge model a model for the gelation is suggested based on the hydrolysis and condensation reactions occurring during synthesis. In addition the optimal composition of the binder system was determined using compressive strength test and solubility experiments. Based on partial charge calculations and experimental data for the hydroxide concentration and the viscosity obtained in this study it is suggested that the polymerization of the inorganic polymer is determined by the concentration of silica species. It was found that the alkalinity has a crucial effect on the condensation process. The optimal potassium hydroxide concentration used in the synthesis of the inorganic polymer was found to be around 3.5 M, which resulted in a compressive strength of the product in the region of 50 MPa.     

拟南芥乙酰羟基酸合成酶与磺酰脲的相互作用以及CoMFA研究

在分子水平上较为详尽地研究了85个磺酰脲类化合物与植物源野生型拟南芥AHAS酶的离体相互作用, 测定了这些化合物对AHAS酶的抑制常数Kiapp. 采用比较分子力场方法(CoMFA)对这些化合物与AHAS酶的相互作用进行了三维构效关系研究, 用此模型预测了检验组10个化合物的pKiapp值, 模型的预测结果与测试结果一致.     

Mathematical Modeling of the Plasma-Chemical Pyrolysis of Methane

A mathematical model was developed for the plasma-chemical pyrolysis of methane, which includes the latest data on the mechanism and kinetics of chemical processes of hydrocarbon pyrolysis and mixing of methane jets with hydrogen heated in an arc plasma torch. The results of calculations on methane conversion and the synthesis of acetylene and its homologues satisfactorily agree with experimental data over a wide range of parameters of the process. It was shown that the methane conversion is initiated via interaction with atomic hydrogen, acetylene is produced through the dissociation of intermediate products involving radicals, and the consumption of acetylene is due to the synthesis of its homologues involving vinylidenecarbene and methylenecarbene in the ground and excited states.     

KINETICS OF SULFUR POISONING IN A FIXED BED FOR F-T SYNTHESIS OVER COMMERCIAL Fe-Cu-KCATALYST

IntroductionSulfurpoisoningofanironcatal}'stisoneofthemostseriousdcactivationproblemsincomn'crcialproductionofsubstitutingnaturalgasforcoalreportedb}'Bartholomc\\ofal.II1andAndersonofal.12I.Thecommercialco-precipitatedFo-Cu-Kcatal\'stpreparedb}'Instituteo…